JP2004526022A - Granular polymer additive and production thereof - Google Patents

Abstract

The following components are prepared from: (a) at least one particulate organic phosphite, organic phosphonites and / or organic phosphonates, and (b) one or more particulate polymer additives that are neither organic phosphites nor organic phosphonites or organic phosphonates. A compressed solidified particulate polymer additive composition in the form of a dried granulate, wherein the particles in said composition are exclusively or substantially exclusively solvated at least to some extent of (a). In situ desolvation of particles of one or more components Drying of the in situ desolvation particles of the particles of one or more components, wherein the dried surfaces of the particles are in contact together and optionally at least partially solvated in (b) The combined surfaces are held together in compacted dry granule form by contacting them together. Also described are compositions of the type described above, except that component (b) is not present.

Description

【Technical field】
[0001]
The present invention provides a polymer additive, i.e., a polymer additive that has been modified such that the additive used in the polymer is in the form of a granular form, such as pellets. About.
[Background Art]
[0002]
A wide variety of particulate additives are used in such polymers for the purpose of improving the properties of the thermoplastic polymer and / or improving the utility of products made from the polymer. Particulate polymer additives of the type used include, for example, antioxidants, flame retardants, flame retardant synergists, heat stabilizers, UV stabilizers, nucleating agents, acid neutralizers or polymer clearers. Substances such as polymer clarifiers are included. Numerous additives can form a cake up in feed hoppers or form ratholes and / or can be fed evenly through metering devices. It would be desirable if the additive could be provided in granular form to facilitate the blending operation, as it may not be possible. Moreover, certain additives often used in the manufacture of polymers, especially finely divided additives such as high melting point nucleating agents and inorganic acid neutralizers, can remove harmful airborne dust during handling and blending operations. Can occur.
[0003]
Various methods for converting polymer additives to granular form have been described. Such methods include melting at least one component in a dry blend of the additives to bind the particles of the blend together, or a special component in the additive blend. The dry blend is compressed or milled after incorporating, for example, waxes, fatty acids, compounds having fatty acid or fatty alcohol chains or metal salts of fatty acids, and the blend is converted into granules or pellets. It is included. Such methods all require the use of external components that act as binders, and such components are not necessarily desired as components in the finished polymer composition and are, in fact, the It can also interfere with product specifications. Moreover, the use of certain previously used binders may degrade the performance characteristics of the polymer being the main player. And, in some cases, the range of additives that can be converted to granules or pellets is a very specific range, and thus cannot be widely used.
[0004]
Some of such conventional developments are described, for example, in US Pat.
[0005]
Relying on the melting of certain components in the blend when converting the blend of two or more particulate polymer additives to a granular form, such as pellets, etc., may also be a special binder component included in the powder blend. This would be of considerable advantage if a method could be found which does not rely on the binding action exhibited by, for example, waxes, fatty acids, compounds having fatty acid or fatty alcohol chains or metal salts of fatty acids. It would be even more highly advantageous if the range of blends of particulate additives that could be converted to granules could be extended so that it was not necessary to rely solely on a particular combination of additives to make the granules, eg pellets.
[0006]
The present invention contemplates achieving such objectives in an efficient and effective manner.
[Patent Document 1]
U.S. Pat. No. 4,957,956
[Patent Document 2]
U.S. Pat. No. 5,597,857
[Patent Document 3]
US Patent No. 5,844,042
[Patent Document 4]
U.S. Pat. No. 5,846,656
[Patent Document 5]
US Patent No. 6,033,600
[0007]
(Brief summary of the invention)
The present invention makes it possible to produce granules of a particulate polymer additive without using conventional binder components or relying on substantial melting of one or more components to be included in the additive blend. It is. In addition, the present invention is believed to have broad utility in that a very wide variety of particulate polymer additives can be used in forming the granular additive compositions of the present invention. Thus, it is not necessary to be limited to the use of particular combinations of additives, but additionally, all of these components can be selected from those widely used in thermoplastic polymers. This, in turn, makes it possible to avoid the use of special components which may be undesirable or undesirable in the finished polymer product in which the present granular additive composition is used.
[0008]
Accordingly, the present invention provides, in one aspect of the invention,
(A) at least one particulate organic phosphite, organic phosphonite and / or organic phosphonate, and
(B) one or more particulate polymer additives that are not organic phosphites, organic phosphonites, or organic phosphonates;
Providing a compacted particulate polymer additive composition in the form of a dry granulate made from the particles of (a), wherein the particles in the granules are exclusively or substantially exclusively The in situ desolvation surfaces of the particles of one or more components are interconnected together and optionally the in situ desolvation surfaces of the particles of one or more components of (b) are interconnected. By being interconnected with each other, they are held in a state of being interconnected to each other in a compacted dry granular form. In other words, the particles of the composition are exclusively or substantially exclusively formerly at least partially solvated particles of one or more components of (a). Undergoes desolvation and drying and optionally the previously at least partially solvated particles of one or more of the components of (b) are held together in a compacted dry granule form by undergoing desolvation and drying ing.
[0009]
The present invention provides, in another aspect of the present invention, a method of making such a compacted granular polymer additive composition in dry granule form, the method comprising:
1) (a) at least one particulate organic phosphite, organic phosphonite or organic phosphonate; (b) one or more particulate polymer additives that are neither organic phosphites nor organic phosphonites or organic phosphonates; and (c) (a) And b) forming a paste from an inert organic processing solvent that can evaporate at a temperature below the lowest melting point or initial melting temperature in (b).
2) compressing and shaping the paste while keeping the solid used to form the paste from melting or substantially not melting, so as to obtain a wet compacted and solidified composition in the form of granules. (Wet compacted composition), and
3) evaporating the processing solvent from the wet compacted solidified composition in granular form and drying it to produce a dry compacted granular polymer additive composition in granular form;
Comprising. When carrying out step 2) of the process, typically a compression apparatus is used, which is operated so that the solid does not melt or substantially melt.
[0010]
Further optional steps that can be used include sieving for the purpose of separating fine particles (if any) that may be present from the dried granulated product mixture, or classifying said granulated product. It is a stage to receive in another way. Such fine particles can be reused as feed to the method.
[0011]
Yet another aspect of the present invention is a
1) (a) at least one particulate organic phosphite, organic phosphonite or organic phosphonate; (b) one or more particulate polymer additives that are neither organic phosphites nor organic phosphonites or organic phosphonates; and (c) (a) And forming a paste from an inert organic processing solvent that can evaporate at a temperature below the lowest melting point or initial melting temperature in (b).
2) compressing and shaping the paste so that the solid used in forming the paste does not melt or substantially does not melt to form a wet compacted composition in granular form;
3) evaporating the processing solvent from the wet compacted solidified composition in granular form and drying it to produce a dry compacted granular polymer additive composition in granular form;
Comprising a compressed solidified granular polymer additive composition in the form of a dry granulate, wherein the additive composition comprises, exclusively or substantially exclusively, one or more of (a) The particles in said granules such that the in situ desolvation surfaces of the particles of the components of the component interconnect together and optionally the in situ desolvation surfaces of the particles of the one or more components of (b) interconnect together Shows the compressive hardness and physical integrity that results from being held together in a compacted dry granule form. In other words, the resulting composition is exclusively or substantially exclusively where the previously at least partially solvated particles of (a) have undergone desolvation and drying and optionally (b) Shows the compression hardness and physical integrity provided by previously at least partially solvated particles undergoing desolvation and drying.
[0012]
Other aspects and features of the present invention will become more apparent from the following description and appended claims.
(More detailed description of the invention)
As used herein, the phrase "the particles in the granules are exclusively or substantially exclusively the in-situ desolvation surface of the particles of one or more components of (a)," as used herein, including the claims. Are interconnected together and, optionally, the in situ desolvation surfaces of the particles of one or more components of (b) are interconnected together and held together in a compacted, dry, granulated form. "Dried particles of one or more components of (a), wherein said granules were at least partially solvated when said granules were dried in situ, but were then desolvated, and optionally also said granules. (B) at least partially solvated when dried in situ, but then desolvated, at which point one or more of the dried particles of one or more components are wholly or almost entirely compacted and solidified Means that are held together in 燥 form. If component (a) happens to be, for example, two different components that meet the definition of (a), the dried particles need to keep the granules in a compacted dry granule form during drying. Only one of the components of (a) which had been solvated at least to some extent but was desolvated at that time. The other components in (a) need not be solvated to any degree. However, even if the two-component dried particles of (a), which had been solvated at least to some extent when dried, but were desolvated at that time, held the granules in a compacted, dry granulated form, Good. In any such case, it is optional whether the particles of one or more components in (b) are solvated at any degree, or if they are at least partially solvated. However, it is also optional whether or not they contribute in any way to the maintenance of the compacted, dried, granular form of the granules. However, the dried particles of component (b), which had been solvated at least to some extent when dried but which had been desolvated at that time, contributed to the retention of the granules in the compacted and dried granule form. The contribution of the particles of (b) with respect to the fact that the granules are kept in the form of compacted and dried granules may be optional.
[0013]
First of all, it will be seen that no components in the additive blend subjected to the treatment according to the invention will melt during the process. Instead, the wet paste produced from the particulate solids and the inert organic processing solvent is compressed, preferably subjected to compression using a compression device, which compression was used to produce the paste. It is performed so that the solid does not substantially melt.
[0014]
In addition, it can be seen that the particles in the granules are not held together by conventional binders, such as waxes, paraffins, fatty acids, compounds having fatty acid or fatty alcohol chains or metal salts of fatty acids. Would. Instead, the binding action in the granules is entirely or substantially entirely based on the solvated or partially solvated component (a) shown above, ie, the granular organic material used to form the granules. Resulting from drying of one or more phosphite, organophosphonite and / or organophosphonate compounds and optionally of one or more solvated or partially solvated particulate components of (b) It is a binding action.
[0015]
Those of ordinary skill in the art, upon reading this disclosure, will note that not all particles of (a) above need be solvated or partially solvated when forming the granules of the present invention. It will be easy to understand. The particles of (a) dispersed in the paste are solvated or partially solvated in sufficient numbers and then subjected to compression and drying in contact with other particles included in the granules. It would suffice if the granules were held together when they formed and formed into granules having sufficient compression hardness and physical integrity for use in conventional polymer additive blending equipment. The same considerations apply to the particles (b), if any, which are solvated or to some extent solvated and which contribute to the binding action which hold the particles together in the form of granules having such properties. Applying to a degree, ie, the particles of (b) need not all be solvated or partially solvated and need not contribute to the binding action. Those of ordinary skill in the art, upon reading this disclosure, will also readily appreciate that not all individual particles in the finished granules of the present invention need be bound together. Alternatively, the number of free particles that are simply encapsulated or trapped within the network of particles that are bound throughout the granules can be a suitably small number. Of course, the number of properly bound particles must be sufficient to exhibit and maintain the compression hardness and physical integrity such that the granules can be used in conventional polymer additive blending equipment. Must.
[0016]
Those of ordinary skill in the art will appreciate, upon reading this disclosure and applying common sense and common sense, the use of two or more different organic phosphites, organic phosphonites, and organic phosphonates as component (a) above, ( It will also be readily appreciated that not all of the components of a) need to contribute to the binding action. Only one of said components exhibits the required binding action and produces a dry finished granule exhibiting compression hardness and physical integrity such that the granule can be used in conventional polymer additive blending equipment. It is sufficient if present in an amount sufficient to provide.
[0017]
An advantageous feature of the present invention is that it is very useful for use as a polymer additive, especially since organic phosphites, organic phosphonites and organic phosphonates exhibit antioxidant properties, especially when used in combination with phenolic antioxidants. In that it is a compound known to be The prior art also indicates that some of such organophosphorus compounds are useful as stabilizers in polymers that are subject to degradation by heat, oxidation and ultraviolet light. Thus, the organophosphorus compound used has at least two functions: (1) to provide bonding strength upon desolvation, compression and drying; and (2) to provide antioxidant and / or stabilizing protection to the finished polymer in which the granules are ultimately used. Is a desirable additive component that fulfills the function of providing
[0018]
Without being limited in theory, such valid evidence is that at least a portion of the particulate phosphorus component in the paste dissolves in the processing solvent, thereby causing the paste to dry and / or dry as a result. It is shown to form or act as a glue or adhesive which serves to bind the particles of the additive together. In other words, the particles contained in the dried, compacted and solidified particles are exclusively or substantially exclusively comprised of at least some of one or more of the organophosphorus components used to form the granular additive composition. It appears that the solvated particles are held together in compacted dry granule form by the adhesive resulting from the desolvation. In some of the granular compositions of the present invention, in addition to the binding due to the residue resulting from the desolvation of component (a) shown above, some of the binding is shown above It may be the result of a residue resulting from the desolvation of one or more of the polymer additives of (b). If there is any such bond due to (b) in addition to the bond due to the residue resulting from (a) being subjected to desolvation, such co-bonding may also be present to the extent possible. Within the scope of the invention, provided, however, that in such cases the physical integrity of the granules is substantially exclusively such that one or more of the organophosphorus compounds of (a) undergoes desolvation. One or more of the resulting residues and one or more of the polymer additives of (b) shown above were provided by one or more of the residues resulting from desolvation. The condition is that it is due to the binding action of one or more kinds of dried glue or one or more kinds of adhesives. If such residues occur, they may be individual residues, or they may be mixed residues, or one or more individual residues And a combination of one or more mixed residues. Briefly, the chemical composition of one or more cohesive glues or one or more adhesives (if any) generated by desolvation is not critical, provided that the substantial bonding is ( a) and one or more such glues or one or more adhesives provided by a) and upon compression and / or drying, combine the particles together with the compression hardness and physical Provided that granules exhibiting integrity are produced.
[0019]
As used herein, the term "substantially exclusive" is used when the physical integrity of the granules is total or at least predominantly or first (i.e., to the highest degree) resulting in (i) producing the granules. One or more of the organophosphorus compounds of (a), or (ii) one or more of the organophosphorus compounds of (a) and one or more components of (b) used in producing the granules. This indicates that both solvated particles are due to the binding action of the particles resulting from undergoing compression and / or drying. As shown herein below, any ingredient known in the art to be a binder produces granules that exhibit desirable compression hardness and physical integrity without use regardless of the mechanism by which it functions. It can occur in the practice of the present invention. In fact, organic phosphites have been used as the sole particulate component of the pastes produced and used in the process of the present invention to produce granules exhibiting the desired compression hardness and physical integrity. Thus, if the practice of the present invention results in bonding due to melting or plastic deformation of the tacky or flexible component in its original state, this is accidental and minimal.
[0020]
The amount of one or more organophosphorus components used in forming the granules can be relatively small compared to other particulate additive components. Thus, the amount of one or more particulate organophosphorus components to be included in the granular additive produced in accordance with the present invention may be as high as 95% by weight, but may be as high as 95% by weight. Preferably, the content of one or more of said organophosphorus compounds in the agent composition is less than 50% by weight, more preferably in the range of 3 to 40% by weight, even more preferably in the range of 5 to 30% by weight, most preferably It is preferably in the range of 15 to 30% by weight, with the balance per 100% by weight of one or more other types of particulate additives such as phenolic antioxidants, amine antioxidants, heat stabilizers, flame retardants , Flame retardant synergists, ultraviolet stabilizers, nucleating agents, acid neutralizing agents, polymer clarifying agents, etc.
[0021]
Each of the particulate components used in forming the granules is at least 50 ° C., more preferably at least 100 ° C., in order to ensure that no substantial melting occurs when forming the granular composition of the present invention. It preferably exhibits a melting point or initial melting temperature of at least 150 ° C. Consistent with this, the processing solvent used is an inert organic solvent which can evaporate at a temperature below the lowest melting point or initial melting temperature of such a mixture of particulate components, preferably at normal atmospheric pressure. Solvent. The particles or particles are bonded together because all the operations used in forming the granule or pellet compositions of the present invention are performed so as to not substantially melt any additive components used in forming such compositions. No bonding by melting is used when doing this. Also, the fact that no viscous or flexible component from the beginning causes plastic binding to bind particles is involved at all, since any component that is known to function in such a manner may It is not necessary to be present in the mixture to be subjected to the treatment according to the invention.
[0022]
The particle size of the particulate components used in forming the paste used in forming the granular additive composition of the present invention is not as large or not as large as the granules or pellets in which these particles are formed. Not important as long as. Thus, as used herein, the term "granular" refers to particles that may range in size from fine powder to small particles, which, in brief, are any particles that can be converted into granules of a desired size. It may be a size.
[0023]
The granules produced according to the present invention may be of any size suitable for use in conventional additive blending or feeding equipment used in connection with polymer blending and / or molding or extrusion processing operations. You may. In addition, the shape of the granules can be any of a variety of suitable shapes, such as cylindrical pellets, spherical pellets, tablets or flakes. In addition, the granules, regardless of shape and size, have the characteristic of generating little dust, exhibit no stickiness and should flow freely. Suitable granules of the present invention exhibit a compression hardness of at least 10 pounds per inch, as measured by the test procedure described herein below.
[0024]
The organic phosphorus-containing compound (a) used in the practice of the present invention includes organic phosphites, organic phosphonites, and organic phosphonates, and their melting point or initial melting temperature is preferably at least 50 ° C. Such an initial melting temperature is, of course, applicable to components exhibiting a melting range different from the melting point, and therefore, the initial melting temperature is the lowest temperature at which a component that melts over a certain temperature range begins to melt. It is. Phosphites, phosphonites and phosphonates are widely known to have antioxidant properties, and many such compounds are commercially available. Suitable organophosphorus compounds exhibiting a melting point or initial melting temperature of at least 50 ° C. are, inter alia, organic organophosphorus compounds as described in US Pat. Nos. 4,094,855, 4,929,654 or 4,956,406. Phosphites, organic phosphonites as described in U.S. Pat. No. 4,233,207 or 4,912,155, and described in U.S. Pat. No. 3,737,486 or 4,524,167. Such organic phosphonates, each of which is incorporated herein by reference. Some specific non-limiting examples of suitable organophosphorus compounds that can be used include the following:
Tris (2,4-di-t-butylphenyl) phosphite;
Bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite;
Tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite;
2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite;
Ethyl bis (2,4-di-tert-butyl-6-methylphenyl) phosphite;
3,9-bis (2,4-di-t-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] -undecane;
3,9-tris (2,4,6-tris-tert-butylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane;
2,2′-ethylidenebis (4,6-di-t-butylphenyl) fluorophosphonite;
2,2 ′, 2 ″ -nitrilo [triethyl-tris (3,3 ′, 5,5′-tetra-t-butyl-1,1′-biphenyl-2,2′-diyl)] phosphite;
Bis (2,6-di-t-butyl-4-carbomethoxyphenyl) phosphorochlorodite;
Bis (2,6-di-tert-butyl-4-carbo-2 ', 4'-di-tert-butylphenoxyphenyl) phosphorochlorodite;
Bis (2,6-di-t-butyl-4-ethylcarbomethoxyphenyl) phosphorochlorodite;
4,4-dimethyl-2,6-dioxaphosphite of 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxy-benzoate;
Cyclic ethylene phosphite of 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate;
cyclic ethylene phosphite of n-octyl-3,5-di-t-butyl-4-hydroxybenzoate;
O-acetylbis (2,6-di-t-butyl-4-carbomethoxyphenyl ester) phosphite;
Bis (2,6-di-tert-butyl-4-carbomethoxyphenyl ester) phosphonic acid;
O- (2,6-di-t-butyl-4-methylphenyl) phenylphosphonochloridite;
O- (2,6-di-t-butyl-4-methylphenyl) -O '-(2,4-di-t-butylphenyl) phenylphosphonite;
O- (2,4-di-t-butylphenyl) -O '-(2,4,6-tri-t-butylphenyl) phenylphosphonite;
O- (2,6-di-t-butyl-4-methylphenyl) -O '-(2,6-di-t-butyl-4-carbomethoxyphenyl) -phenylphosphonite;
O- (2,4,6-tri-t-butylphenyl) phenylphosphonite;
O, O'-bis- (2,6-di-t-butyl-4-carbomethoxyphenyl) phenylphosphonite; and
Bis (2,4-dicumylphenyl) pentaerythritol diphosphite.
[0025]
If desired, it is also possible to use mixtures of two or more of the abovementioned compounds. More preferred phosphorus additives are tris (2,4-di-t-butylphenyl) phosphite (melting point: about 182-188 ° C.) and bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite (Melting point: about 160-175 ° C), and tris (2,4-di-t-butylphenyl) phosphite is most preferred.
[0026]
For ease of reference, regardless of whether the phosphorus compound used herein as component (a) is used alone or as a combination of two or more such compounds, it will be referred to herein as "phosphorous compound" It is called "phosphorus component".
[0027]
One or more of the components of (b) shown above, ie, one or more components different from the one or more components of (a) shown above, and a variety of particulate polymer additives as one or more particulate additives Any of the agents can be used. The criterion used when selecting one or more components of (b) shown above is that the component is higher than the boiling point or the final boiling range of the processing solvent and the mixture of (a) and (b) is mixed. Exhibits a melting point or initial melting temperature (preferably at least 50 ° C., more preferably at least 100 ° C., and most preferably at least 150 ° C.) higher than the highest temperature exposed during the pressing and drying steps Being a particulate additive and a material that does not exhibit any stickiness or flexibility, during which it is said that other particulate matter will stick or embed to any significant degree during processing, e.g., due to plastic deformation under pressure. And that it is suitable for use as an additive to improve the processability, properties and / or performance of the finished polymer in which it is used. Thus, generally, one or more of the particulate additives used as component (b) are free from melting under the individual conditions selected for use in the compaction and drying of the paste. It should be a flowing particulate additive. Possible types of polymer additives include, inter alia, antioxidants, ultraviolet or light stabilizers, nucleating agents, acid neutralizers, polymer clarifiers, flame retardants, flame retardant synergists, fillers and reinforcing agents, Metal deactivators or passivators as well as various other functional additives. There is a wealth of information in the art on polymeric additives that meet such criteria, and therefore, the burden of this disclosure on a vast list of such additives is almost nothing. Will not be obtained. A recent patent, US Pat. No. 6,060,543, provides a more-than-adequate list of typical polymer additives from which the criteria are met. The ingredients could be selected. Thus, a suitable antioxidant could be found in the disclosure shown in column 34, line 28 to column 37, line 35 of the patent. There is a list of UV absorbers and light stabilizers in column 37, line 36 to column 40, line 2 of the patent, from which a component meeting the criteria could be found. Suitable metal deactivators or passivators may be found in the disclosure shown in column 40, lines 3-12 of said patent. Column 42 lines 31 to 38 of said patent list nucleating agents and column 42 lines 39 to 43 list fillers and reinforcing agents, from which types meet the criteria. Could be selected. Appropriate thiosynergists, peroxide scavengers, polyamide stabilizers and basic compounds are listed in the list shown in column 41, lines 49 to 67 and column 42, lines 29 to 30 of said patent. Basic co-stabilizers could be found. All such sections of the patent are incorporated herein by reference, provided that each component selected from the list should meet the criteria.
[0028]
Some non-limiting examples of additives of type (b) that can be used in forming the compositions of the present invention include the following:
A) One or more particulate sterically hindered phenolic antioxidants, for example 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 4,4′-methylenebis (2,6-di-t-butylphenol), crystalline tetrakis [3- (3,5-di- t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane, n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2-bis [3 ′, 5'-di-tert-butyl-4'-hydroxyphenylpropionyloxy-ethoxyphenyl] propane, triethylene glycol-bis [3- (3'-tert-butyl-4'-hydroxy-5 Methylphenyl) propionate and 1,5-bis (3 ', 5'-di -t- butyl-4'-hydroxy-phenylpropionyl) -3' Chiopentan like.
B) One or more particulate sterically hindered amine stabilizers, for example bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidinyl) Succinates and the stabilizers indicated in column 4, line 29 to column 23, line 36 of U.S. Pat. No. 5,597,857, which section is incorporated herein by reference. And similar stabilizers that meet the above criteria.
C) One or more granular nucleating agents, such as sodium 2,2'-methylenebis (4,6-di-t-butylphenyl) phosphate, sodium adipate, sodium diphenylacetate and sodium benzoate. Sodium benzoate is a preferred nucleating agent.
D) One or more granular polymer clarifiers, for example 1,3: 2,4-bis (3,4-dimethylbenzylidene) sorbitol (Millad 3988; Millikan Chemical), 1,3: 2,4-bis ( p-methylbenzylidene) sorbitol (Millad 3940; Millikan Chemical) and 1,3: 2,4-di-O-benzylidene sorbitol (Millad 3905; Millikan Chemical) and the like.
E) One or more particulate acid neutralizing agents, such as metal oxides (eg, zinc oxide, magnesium oxide and titanium dioxide), metal carbonates (eg, calcium carbonate and magnesium carbonate) and natural or synthetic hydrotalcites (eg, Magnesium hydrotalcite, such as DHT-4A, DHT-4V, DHT-4C (all available from Kyowa Chemical Co); Hysafe 539 and Hysafe 530 (available from JM Huber Corporation); L-55R acid neutralization And zinc hydrotalcite such as ZH4-A (available from Kyowa Chemical Co.) Suitable acid neutralizing agents are DHT-4A, DHT-4V and DHT-4C. .
F) One or more particulate flame retardants such as decabromodiphenyl oxide, tetrabromobisphenol-A, hexabromocyclododecane, SAYTEX ™ 8010 ™ flame retardants, brominated aromatic compounds having a patented structure (Albemarle Corporation), tetradecabromodiphenoxybenzene, tetrabromocyclooctane, ethylenebistetrabromophthalimide, bis (2,3-dibromopropyl ether) of tetrabromo-bisphenol-A, bis (2,2) of tetrabromobisphenol-S 3-dibromopropyl ether), hexabromobenzene, melamine, ammonium polyphosphate, and particulate organophosphorus flame retardants, such as high melting nitrogen-containing diphosphine compounds, such as U.S. Pat. No. 5,281,637. And the disclosures of such compounds and their preparation are incorporated herein by reference.
G) One or more particulate flame retardant synergists, such as antimony trioxide, sodium antimonate and sodium borate.
H) One or more particulate heat stabilizers, such as dibutyltin mercaptopropionate (Barostab M36; Barlocher GmbH), dioctyltin mercaptopropionate (Barostab OM36; Barlocher GmbH) and high molecular weight dibutyltin maleate (Barostab MS; Barlocher GmbH).
I) One or more particulate fillers or reinforcing agents such as silica, alumina, silica-alumina, natural and synthetic zeolites, montmorillonite, short glass fibers and metal whiskers.
[0029]
The binding qualities of the phosphorus component in forming the granulated product of the present invention, i.e., upon completion of the drying step, normal handling, transport, and molding or extrusion of the molten polymer blend. It is used in an amount sufficient to produce granules having sufficient compression hardness and physical integrity to withstand the mixing operations used in forming the dry polymer blend suitable for use at times. Preferably, the content of the phosphorus component in the dried granular product is at least 3% by weight. More preferably, the content of the phosphorus component is at least 5% by weight, and even more preferably at least 10% by weight. Most preferably, the content of the phosphorus component is at least 15% by weight.
[0030]
The processing solvent used is preferably a solvent in which the phosphorus component used exhibits a minimum solubility of 5 grams per liter of solvent. More preferably, the minimum solubility of the phosphorus component in the solvent is 10 grams per liter of solvent, most preferably 20 grams per liter of solvent at the temperature that produces the paste. However, preferably, the solvent used is a solvent that limits the dissolution of the phosphorus component. Thus, it is desirable to use a solvent in which the maximum solubility of the phosphorus component is 300 grams per liter of solvent, more preferably 200 grams per liter, and a maximum solubility of 100 grams per liter. Most preferably, grams. Said solubility is preferably the solubility measured at a temperature in the range of 20 ° C. to 70 ° C., most preferably the solubility measured at the temperature at which the paste forms granules.
[0031]
It should be noted that granules or pellets according to the process of the invention can in principle be obtained even with phosphorus component / treatment solvent pairs whose solubility is greater than the maximum values indicated above. In most cases, adjustments to the solvent concentration can be made to provide a suitable paste.
[0032]
When producing such a paste, a substantially uniform mixture is formed by dry blending each of the particulate components of (a) and (b) together in a dry blender. After that, the processing solvent is preferably added and the resulting wet mixture is mixed to produce a substantially uniform paste. However, it is also possible to use other modes of addition. For example, when forming a mixture to be granulated, such as a mixture of a suitable phosphite, a high melting acid neutralizer, a high melting nucleating agent, and a processing solvent, the components dried before adding the processing solvent You do not need to keep them together. Alternatively, it is also possible to mix the acid neutralizing agent and the nucleating agent to form a mixture, to which the solvent and the phosphite are added simultaneously or in any order. If desired, it is also possible to combine one dried component with the processing solvent and then add the other two dried components. Yet another approach is to continuously combine the materials in small portions just prior to producing granules. Briefly, the order or mode of addition is not critical at all, and any method that results in the formation of a substantially uniform paste can be used.
[0033]
Irrespective of the order or mode of addition, the phosphorus component is unevenly combined with one or more other particulate components such that the phosphorus component is substantially uniformly dispersed in the paste prior to undergoing the granulation process. It is preferable to disperse without dispersion.
[0034]
If the paste to be produced contains components which are antioxidants or nucleating agents, it is very suitable that the phosphorus component can be dissolved in the processing solvent at the temperature at which the paste is produced. If any other particulate component is soluble in the processing solvent at the temperature at which the paste is formed, such dissolution will not necessarily reduce the compression hardness of the resulting granules.
[0035]
Moreover, when the phosphorus component used is a mixture or combination of two or more phosphorus compounds, the low dust of the present invention is provided if only one such phosphorus component compound exhibits a solubility in the above range. A composition can be formed.
[0036]
Any of a wide variety of inert organic processing solvents that can evaporate at the lowest melting point or below the melting range of the particulate components used can be used. For example, if the component with the lowest melting point melts at, for example, 55 ° C., the processing solvent used should be capable of evaporating entirely at temperatures below 55 ° C., preferably at ambient atmospheric pressure. However, if necessary or desired, the drying may be carried out under reduced pressure, provided that the applied vacuum does not lead to a pronounced decompaction of the shaped granules.
[0037]
Non-limiting examples of types of processing solvents that can be used include hydrocarbons, eg, halogen substituted hydrocarbons, such as alkanes, cycloalkanes, alkenes, cycloalkenes, and aromatic hydrocarbons, ethers, alcohols and ketones. Some illustrative examples of such solvents include pentane, hexane, isopentane, heptane, isohexane, 2-methylheptane, cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, benzene, toluene, chloroform, methylene chloride, diethyl Includes ether, 2-ethoxypropane, tetrahydrofuran, 1,4-dioxane, ethyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone and mixtures thereof. Hexane, isohexane and cyclohexane are preferred.
[0038]
Nevertheless, if all of the particulate components exhibit a melting point or initial melting temperature significantly above 150 ° C., for example 180 ° C. or higher, an inert evaporable at atmospheric pressure and below 150 ° C. It is preferable to use a processing solvent that is an organic solvent. In such cases, it is possible to use inert processing solvents that exhibit a boiling point above 150 ° C. or a final boiling temperature at atmospheric pressure, but more expensive drying when using such higher boiling solvents. It may be necessary to use methods and equipment, such as vacuum drying, depending on the melting point or minimum melting temperature of the granules to be treated. In addition, with vacuum drying, some disintegration of the wet compacted granules can occur unless it is performed under properly controlled conditions.
[0039]
During the granulation process, the phosphorus component and one or more other particulate additives and the processing solvent are converted into a substantially uniform paste. Preferably, the consistency of the paste is such that the paste can be extruded without the need to apply excessively high operating pressures or temperatures. Melting and / or melting will result. Thus, when the wet paste is processed and extruded through a die press, the internal temperature of the apparatus and the temperature of the paste may be below the temperature at which melting and melting of the particles can occur. The granulation process should be performed to keep it. Suitable methods for performing the operations in such a manner are, of course, well known to those of ordinary skill in the art.
[0040]
The ratio of the selected particulate additive components of (a) and (b) to the processing solvent used is any ratio provided that a compressible or compactible and moldable paste results without melting of any of the components. You may. While in no way limiting the range of ratios suitable for use in forming a suitable paste, generally the weight ratio of solvent to total additives is such that the solvent is in the range of 3 to 20 parts by weight per 100 parts by weight of total additives. It is preferred that By total additives is meant all of the particulate additives used in forming the paste and the resulting granules or pellets.
[0041]
One or more granulation methods can be used when forming granules from the paste (mixture of additive powder moistened with solvent). One of the most convenient methods is to extrude the paste through a suitably sized perforated die plate to produce one or more strands or "noodles" and cut it. Into pellets of the desired length. Such pellets are typically cylindrical, the size and shape of the cross section being determined by the characteristics of the holes drilled in the die plate. The cross-sectional shape of the pellets generally does not significantly affect its compression hardness, and therefore does not significantly affect the dust properties of the granulated mixture. A wide range of cross-sectional shapes can be used. Suitable cross-sectional shapes include circles, ellipses, triangles, rectangles, pentagons, hexagons, other polygons and semi-circles, and other shapes having one or more curved sides. The cross-sectional area is preferably in the range of 1 to 75 square millimeters. Cross-sectional areas ranging from 3 to 20 square millimeters are more preferred. Cross-sectional areas ranging from 3 to 9 square millimeters are most preferred. Preferably, the length distribution of the pellets is in the range of 0.5 to 10 times the effective pellet diameter, the average pellet length is in the range of 1 to 5 times the diameter of the pellet, and the pellet is in the range of 2 to 3 times. Average length is most desirable. "Effective pellet diameter" means the maximum cross-sectional dimension of the pellet. For example, the effective pellet diameter for a cylindrical pellet is the diameter of its circular cross section, while the effective pellet diameter for a square pellet is the diagonal distance from one corner of the square cross section to the opposite corner. is there.
[0042]
It is convenient and thus preferred to produce cylindrical pellets. However, it is also possible to use other granulation methods instead of or in addition to cylindrical pellets produced using a die plate. For example, it is possible to use a Marumurizer (LCI Corporation) for the purpose of converting a cylindrical pellet into a roughly spherical pellet. The preferred, more preferred and most preferred cross-sectional areas of the pellets thus produced are the same as for the extruded pellets as described above.
[0043]
Granules produced by the process of the present invention typically provide the advantage of having a very low dust generation feature. However, in some cases, particles less than 0.25 millimeters in size may result in some broken granules or other fines that generate dust by the granulation process itself. Is desirably removed. This can be easily achieved by sieving the dried granules through a screen with 0.25 millimeter openings, such as a screen of US Standard No. 60. If desired, other suitable granule classification methods can be used to remove such small particles. When it is important for the user of the present granules that the degree of dust generation is low, it is desirable that the amount of particles less than 0.25 millimeters contained in the present granules is at most 3% by weight. Preferred low dust granules of the invention contain less than 0.25 millimeters of particles less than 0.5% by weight, more preferably less than 0.1% by weight.
[0044]
The compaction or compaction and shaping to form granules or pellets from the paste is preferably a pellet mill, i.e. typically a device for kneading the contents with a roller and passing the contents through an orifice of a die. This is performed using. Such pellet mills are typically cooled from the ambient room temperature (eg, 20 ° C.) to 5 ° C. below the boiling temperature of the processing solvent used, which in turn causes the melting temperature of any particulate matter in the paste to exhibit. (Which is lower than the lowest melting temperature in). For example, if the processing solvent used is cyclohexane (boiling point = 81 ° C.), the die temperature should typically be in the range of 20 to 76 ° C. In order to ensure that at least some of the processing solvent remains in the pellets when the pellets are being formed or formed, the pellet mill is preferably pumped at least 10 times above the normal boiling temperature of the processing solvent. Operate at a die temperature that is lower by at least 20 ° C, more preferably at least 20 ° C. Since pellet mills typically do not have external or internal heaters or electrical or electronic temperature control, the heating rate due to friction generated as the paste flows through the orifice of the die and the pellet mill The balance between the heat that is naturally lost from the die determines the actual die temperature for a given paste composition. In practice, for a given composition, the desired die temperature is achieved by appropriately setting the two operating variables as follows: 1) the concentration of the processing solvent (the temperature of the die 2) Aspect ratio (ie, the ratio of the working length (also referred to as the "pressway" length) divided by the diameter of the die hole]. Die temperatures typically increase with increasing aspect ratio. The temperature of the die can also be affected by other operating parameters of the pellet mill (eg, rotor speed or paste feed speed), but their effect on die temperature is generally the concentration of solvent in the paste. And relatively smaller than the aspect ratio of the die hole.
[0045]
Other types of equipment that can be used in forming granules or pellets from the paste upon compression or consolidation and molding include paste extruders and powder extruders. Such devices typically operate in a manner similar to a pellet mill except that the action of a rotating screw is used instead of using a roller for this purpose when passing the contents through a die hole.
[0046]
In the practice of the present invention, the temperature of the paste subjected to compression or compression solidification and molding is higher than the melting temperature of the present granules or pellets or the melting temperature of one or more solid additive components contained therein. It must not be at a high temperature.
[0047]
It will be appreciated and appreciated that the compression or compaction and molding may be performed in any order. As described above, after the paste in a wet state is formed into a large-sized granule, the large-sized granule can be subjected to compression to produce a compacted granule. Typically, however, the wet paste is compressed by passing it through an orifice of a die, for example by extrusion, and then the extruded product is cut and shaped into granules.
[0048]
For the mixture wet with the solvent before undergoing the granulation operation, the weight percentage of the processing solvent in the wet paste mixture is in the range of 1 to 20% by weight, preferably 2 to 10% by weight. It is preferable to set the range. Most preferably, the amount of processing solvent contained in the wet paste mixture prior to undergoing the granulation operation is in the range of 5 to 10% by weight.
[0049]
The granules can vary in the relative ratio of one or more of component (a) to one or more of component (b). For example, it is possible to use these components in a high ratio such as 99.9: 0.1 by weight ratio of (a) :( b). Range from 3:97 to 40:60. Preferably, the weight ratio of (a) :( b) is in the range of 5:95 to 30:70, most preferably in the range of 15:85 to 30:70. In one embodiment of the present invention, the solids contained in the granules are all particles of (a), i.e. (i) one or more organic phosphites, (ii) one or more organic phosphonites, or (iii) One or more organic phosphonates, or any mixture of any two or all three of (iv), (i), (ii) and (iii), wherein the particles in the composition are Exclusively or substantially exclusively, at least some solvated particles of (a) are bound together by undergoing drying and desolvation, ie, bound together by apparently desolvated residues. Are held together in the form of compacted dry granules.
[0050]
Prior to using or storing the granules or pellets, all or almost all of the processing solvent should be removed by drying. If solvent remains, the amount will typically be trace, for example, the amount of residual processing solvent will be less than 100 ppm (weight / weight). The drying process can be carried out at room temperature or at elevated temperature, a temperature in the range of 60 ° C. to 105 ° C. is most convenient, provided, of course, that the temperature of drying is not higher than and does not exceed the melting temperature of the granules. The melting point is not higher than the melting temperature of one or more of the additive components. Numerous types of dryers are suitable, such as, for example, a forced air oven, a vacuum oven, a fluid bed dryer, a Wyssmont dryer, or a belt dryer. It will, of course, be appreciated that the compressed wet granules need not be placed under the compressive force applied thereto when drying. Also, the dried granules are essentially composed of components (a) and (b), and to the extent that they have been modified, the solvation, desolvation and compaction are based on their original physical state and It will also be understood that this may affect the chemical composition, but only if any. Generally speaking, there is no component other than components (a) and (b) and the processing solvent present in the paste used in forming the dried granular composition of the present invention. If it is desirable to include a liquid in the composition of the present invention as a polymer additive, it should form a single-phase liquid with the processing solvent and should also have the properties of the dried granules when processing the paste. Should not have any adverse effects. In addition, if any such liquids are used as polymer additives, they should not have or have substantially no binding properties and will result in the granules being dried and compacted. It should be able to be dried under the drying conditions used in the drying. Usually, the amount of such initially liquid, dry, unbound polymer additive should not exceed 20% by weight of the dried granules, based on the dry residue.
[0051]
A suitable index that indicates that a granular material has a tendency to generate dust is the compression hardness of the particles. The term "compression hardness" as used herein is defined as a measure of the friability resistance of the granules,
1) Place the granules between two unpadded parallel steel plates such that the length dimension of the pellets is parallel to the steel plates,
2) Apply load to the upper plate while holding the lower plate fixed until the pellets begin to collapse, and
3) divide the load obtained in step 2) by the length of the granule specimen;
To measure. Compression hardness is generally expressed in units of kg / cm (pounds / inch). Generally, only granules having a low tendency to generate dust are granules having a high compression hardness, whereas a low compression hardness indicates that the tendency to generate dust is strong. Good crush resistance properties are obtained when the compression hardness is greater than 0.89 kg / cm (5 lb / in), compression hardness greater than 1.79 kg / cm (10 lb / in) is more preferred, A compression hardness of greater than 15 pounds per inch is most preferred. When performing the procedure, at least 13 particles are randomly selected from a given batch of dried granules, and each of the particles is individually subjected to the procedure and tested for 13 or more individual particles. The average compression hardness should be calculated from the results obtained for each of the above.
[0052]
When producing or forming granules, such as pellets, according to the method of the present invention, it is often preferred that the phosphorus component be partially, but not completely, dissolved in the processing solvent. However, in some cases, for example, when the proportion of phosphorus compounds in the blend of (a) + (b) is relatively small (eg, around 3 to 5% by weight), all of the phosphorus components are in solution. May be advantageous. Examination of the dried granules of the present invention by scanning electron microscopy (SEM) typically shows that the particles are tightly packed together, i.e., if there is any dried glue or adhesive generated during the process. Even if it does, it is usually not easy to detect by SEM. If essentially complete solvation of the phosphorus component occurs, followed by desolvation, the particles of the desolvated phosphorus component in the dried granules have an irregular shape and are used in the process. It may have a different size than the previous original size. It should be clearly understood and appreciated that such features related to SEM observation are not to be construed as limitations or requirements of the present invention. As long as at least the phosphorus component undergoes some solvation during the process and at least that solvated portion of the phosphorus component undergoes drying while the particles in the granules are in intimate compression contact with each other, the resulting The dried granules of the present invention exhibit compression hardness and physical integrity suitable for use in conventional dry blending operations.
[0053]
The following examples illustrate the invention but do not limit the scope of the invention.
Example I
10 pounds of tris (2,4-di-t-butylphenyl) phosphite [IRGAFOS 168 powder; Ciba Specialty Chemicals Corporation) and 0.59 kg (1.30 pounds) of cyclohexane together. A homogeneous mixture was obtained by tumble blending for minutes. This mixture was processed to give cylindrical pellets as follows: 1) KAHL Model 14 at a feed rate of 58-68 pounds / hour of the mixture. -175 pellet mill, which is equipped with a perforated die plate having a diameter of 3 mm and a pressway length of 10.5 mm, which was operated at a rotor speed of 100 rpm, and The output of the pellet mill is collected in a stainless steel pan, 3) the output material is placed in a forced air oven and dried for 2 hours by operating the oven under a nitrogen atmosphere at 105 ° C, and 4). The dried material is dry sieved through a US Standard No. 8 screen to process fines (ie, a No. 8 screen). Removing small particles) as through the over down. The resulting product is composed of cylindrical pellets nominally 3 mm in diameter, and the particles exhibit a compression hardness of 13-14 lb / in (2.32-2.50 kg / cm) (compression Hardness test method), which was obtained in a yield of about 83%. The granules exhibited a low degree of dust generation and had good powder flow properties and therefore exhibited good metering and handling properties.
Example II
4.35 kg (9.60 lb) of sodium benzoate powder (44 micron low dust grade from Total Specialty Chemicals), 2.18 kg (4.80 lb) of DHT-4A hydrotalcite powder [Kyowa Chemical Industry (Obtained from Kyowa Chemical Industry Co., Ltd.) and 1.60 pounds of IRGAFOS 168 phosphite powder (obtained from Ciba Specialty Chemicals) were tumble blended for 6 minutes. After adding a processing solvent (1.09 kg [2.40 pounds] of cyclohexane) to the powder blend, the mixture was subjected to a tumble blend for 6 minutes to obtain a uniform mixture for pelletization. A pelletizing operation was performed using a Kahl Model 14-175 pellet mill equipped with a die plate having a hole having a diameter of 3 mm and a pressway length of 10.5 mm and operating at a rotor speed of 100 rpm. . The feed mixture was metered into the pellet mill equipped with a twin-screw volume metering device at a feed rate of 11.79 kg / hr (26 lb / hr). Collecting the output from the pellet mill in a stainless steel pot, placing it in a forced air oven, and operating the oven under a nitrogen atmosphere at 105 ° C. for 1.5 hours. Then, the treatment solvent was removed by evaporation. The dried product was dry sieved through a US Standard No. 8 screen to remove fines (ie, particles small enough to pass through the No. 8 screen). The resulting product was obtained in 93-95% yield. This form was a white cylindrical pellet with a nominal diameter of 3 mm and a length in the range of 1 mm to 6 mm. The product had a high compression hardness, i.e., 22-33 pounds per inch (3.93-5.89 kg / cm), and exhibited low dust generation and excellent powder flow.
[0054]
Examples I and II demonstrate that previously at least partially solvated organic phosphites that have undergone desolvation and drying act as very effective binding components to hold the particles together, and thus the desired physical integrity This shows that it is not necessary to use a conventional binder nor to melt the components when producing granules having properties such as pellets.
[0055]
Thus, in the practice of the present invention, there is no need to use any components that melt, such as low melting point binders or components that are viscous or soft (such as putty) in the wet state, without the need for polymer additives. It will be appreciated that the compositions are prepared and provided in granular form. Similarly, the polymeric additive compositions are prepared and provided in granular form without the need for fatty acids or fatty alcohols or their derivatives, such as metal salts of stearic acid (eg, calcium stearate, magnesium stearate or zinc stearate). . However, it is possible, but not preferred, to include such salts in the compositions of the present invention that tend to have the ability to neutralize acids, provided that they are used in the practice of the present invention (a). Provided that one or more previously at least partially solvated organophosphorus components do not interfere with the bond created by subjecting them to desolvation and drying, and furthermore their presence uses the granules. Provided that the individual polymers to be treated are not adversely affected.
[0056]
The compacted particulate polymer additive composition of the present invention is a complete granule formed by the particles being packed together by undergoing drying while in intimate contact with each other when the particles are at least partially solvated. It will be further understood that it is configured.
[0057]
Unless otherwise specified, the use of the part of speech "a" or "an" herein is not intended and limited to the single elements pointed to by the part of speech in a claim. Should not be dried as. Rather, the use of the part of speech "a" or "an" herein is intended to cover one or more such components unless the text clearly indicates otherwise.
[0058]
It will also be understood that the terms "substantially" and "substantially" refer to neither a chemical process nor an operation being usually absolute. "Substantially" means of significant significance, value, degree, quantity, or degree, as defined by the standard dictionary upon which this specification relies. Such a definition is arguably clear enough for anyone with ordinary skill in science and technology to readily understand. Thus, instead of describing a variable as absolute, it is more realistic to describe the variable as being substantially near the represented variable. For example, when describing whether or not melting will occur, a molecule of a substance may melt in a negligible number, but such melting may also have a significant detectable effect on the results achieved. Has no significant effect. Thus, it is more realistic to indicate that the word should not be melted or substantially melted in order to avoid hypertechnical and formalistic manipulation. Therefore, in any and all respects, this material should be read with the application of common sense and common sense.
[0059]
Where reference is made to reactants and components using chemical names or formulas herein or elsewhere in the claims herein, whether or not the reference is singular or plural, It should be understood that prior to contacting another substance (referred to by its chemical name or type) (such as another component or solvent), it identifies them as being present. It does not matter if any preliminary chemical changes, chemical transformations and / or chemical reactions (if any) occur in the resulting mixture or solution, since such changes, transformations and / or reactions are designated This is because it occurs naturally as a result of combining the components under the required conditions in accordance with the present disclosure. Briefly, components are identified as materials to be brought together in connection with forming a mixture to be used in performing a particular operation. In addition, it may be possible that in the claims set forth herein, reference is made to a substance, component and / or material in its current tense (“comprising” or “is”), Reference is made to a substance, component or material as if it were present at a time immediately prior to first contacting, blending or mixing it with one or more other substances, components or materials in accordance with the present disclosure. It points.

Claims (47)

The following ingredients:
(A) at least one particulate organic phosphite, organic phosphonites and / or organic phosphonates, and (b) one or more particulate polymer additives that are neither organic phosphites nor organic phosphonites or organic phosphonates;
Wherein the particles in said granules are exclusively or substantially exclusively particles of one or more components of (a). In-situ desolvation surfaces of the particles interconnected together, and optionally the in-situ desolvation surfaces of the particles of one or more components of (b) interconnected together in a compacted, dry, granular form. A composition that has been retained in a dry state. The composition of claim 1 wherein the components (a) and (b) exhibit a melting point or initial melting temperature of at least 100 ° C. The composition of claim 1 wherein the components (a) and (b) exhibit a melting point or initial melting temperature of at least 150 ° C. The composition according to claim 1, wherein the component (a) used is at least one organic phosphite. The composition according to claim 4, wherein the organic phosphite is tris (2,4-di-t-butylphenyl) phosphite. Each polymer additive of (b) used exhibits a melting point or initial melting temperature of at least 50 ° C. and at least one of said polymer additives of (b) is a hindered phenolic antioxidant, a nucleating agent The composition according to claim 1, which is a polymer clarifier, an acid neutralizer or an ultraviolet or light stabilizer. 7. The composition according to claim 6, wherein component (a) used is at least one organic phosphite. Component (b) used is (i) one or more nucleating agents, (ii) one or more polymer clarifying agents, (iii) one or more acid neutralizing agents, and (iv) (i) ), (Ii) and (iii) are selected from the group consisting of mixtures of any two or all three, and each of said components (b) used has a melting point or initial melting temperature of at least 200 ° C. The composition according to claim 1, which shows: 7. The composition according to claim 6, wherein component (a) used is at least one organic phosphite. The component (b) used was (i) sodium benzoate, (ii) 1,3: 2,4-bis (3,4-dimethylbenzylidene) sorbitol, (iii) 1,3: 2,4-bis ( (p-methylbenzylidene) sorbitol, (iv) 1,3: 2,4-di-O-benzylidene sorbitol, (v) an acid neutralizing agent that is at least one metal oxide, (vi) at least one metal An acid neutralizing agent which is a carbonate, selected from the group consisting of (vii) at least one natural or synthetic hydrotalcite and (viii) a mixture of any two or more of all of (i) to (vii). 2. The composition of claim 1, wherein the composition is prepared. The composition according to claim 10, wherein the component (a) used is at least one organic phosphite or at least one organic phosphonite or both. The composition according to claim 10, wherein the component (a) used is tri (2,4-di-t-butylphenyl) phosphite. A method for producing a compressed solidified granular polymer additive composition in the form of a dry granule,
1) (a) at least one particulate organic phosphite, organic phosphonite or organic phosphonate; (b) one or more particulate polymer additives that are neither organic phosphites nor organic phosphonites or organic phosphonates; and (c) (a) And forming a paste from an inert organic processing solvent that can evaporate at a temperature below the lowest melting point or initial melting temperature in (b).
2) compressing and shaping the paste so that the solid used in forming the paste does not melt or substantially does not melt to form a wet compacted composition in granular form; 3) evaporating the processing solvent from the wet compacted solidified composition in granular form and drying it to produce a dry compacted granular polymer additive composition in granular form;
A method comprising: 14. The method of claim 13, wherein (a) and (b) exhibit a melting point or initial melting temperature of at least 100C. 14. The method of claim 13, wherein (a) and (b) exhibit a melting point or initial melting temperature of at least 150 ° C. 14. The method according to claim 13, wherein (a) used is one or more organic phosphites. 17. The method of claim 16, wherein said one or more organic phosphites is tris (2,4-di-t-butylphenyl) phosphite. The (b) used is (i) at least one hindered phenolic antioxidant, (ii) at least one nucleating agent, (iii) at least one polymer clarifying agent, (iv) at least one (V) at least one ultraviolet or light stabilizer, and (vi) a mixture of any two or more of all of (i) to (v). 13. The method according to 13. 19. The method according to claim 18, wherein (a) used is one or more organic phosphites. Each of (b) used exhibits a melting point or initial melting temperature of at least 100 ° C. and (b) comprises (i) at least one nucleating agent, (ii) at least one polymeric clarifying agent, (iii) 14. The method of claim 13, wherein the method is selected from the group consisting of at least one acid neutralizing agent and a mixture of any two or all three of (iv), (i), (ii), and (iii). 21. The method according to claim 20, wherein (a) used is one or more organic phosphites. (B) is (i) sodium benzoate, (ii) 1,3: 2,4-bis (3,4-dimethylbenzylidene) sorbitol, (iii) 1,3: 2,4-bis (p-methylbenzylidene) Sorbitol, (iv) 1,3: 2,4-di-O-benzylidene sorbitol, (v) an acid neutralizer that is at least one metal oxide, and (vi) at least one metal carbonate. 14. An acid neutralizer, selected from the group consisting of (vii) at least one natural or synthetic hydrotalcite and (viii) a mixture of any two or more of all of (i) to (vii). The described method. 23. The method according to claim 22, wherein (a) used is at least one organic phosphite or at least one organic phosphonite or both. 23. The method according to claim 22, wherein (a) used is tri (2,4-di-t-butylphenyl) phosphite. 14. The method of claim 13, further comprising separating fine particles from the dried, compacted, particulate polymer additive composition in granular form. 1) (a) at least one particulate organic phosphite, organic phosphonite or organic phosphonate; (b) one or more particulate polymer additives that are neither organic phosphites nor organic phosphonites or organic phosphonates; and (c) (a) And forming a paste from an inert organic processing solvent that can evaporate at a temperature below the lowest melting point or initial melting temperature in (b).
2) compressing and shaping the paste so that the solid used in forming the paste does not melt or substantially does not melt to form a wet compacted composition in granular form; 3) evaporating the treatment solvent from the wet, compacted, solidified composition in granular form and drying it to produce the additive composition in dry granular form;
Wherein the at least partially solvated particles of (a) have undergone drying and desolvation, and optionally, An additive composition in the form of a dry granule, having at least some solvated particles of (b) subjected to drying, resulting in exclusive or substantially exclusive compression hardness and physical integrity . 27. The composition of claim 26, wherein (a) and (b) exhibit a melting point or initial melting temperature of at least 100C. 27. The composition of claim 26, wherein (a) and (b) exhibit a melting point or initial melting temperature of at least 150C. 27. The composition according to claim 26, wherein (a) used is at least one organic phosphite. 30. The composition of claim 29, wherein said at least one organic phosphite is tris (2,4-di-t-butylphenyl) phosphite. (B) used is (i) at least one hindered phenolic antioxidant, (ii) at least one nucleating agent, (iii) at least one polymer clarifying agent, (iv) at least one Selected from the group consisting of one acid neutralizer, (v) at least one ultraviolet or light stabilizer, and (vi) a mixture of any two or more of all of (i) to (v). 27. The composition of claim 26. 32. The composition according to claim 31, wherein (a) used is at least one organic phosphite. (B) used exhibits a melting point or initial melting temperature of at least 200 ° C. and comprises (i) at least one nucleating agent, (ii) at least one polymeric clarifier, (iii) at least one 27. The composition of claim 26, wherein the composition is selected from the group consisting of an acid neutralizing agent, and a mixture of any two or all three of (i), (ii) and (iii). 32. The composition according to claim 31, wherein (a) used is at least one organic phosphite. (B) used was (i) sodium benzoate, (ii) 1,3: 2,4-bis (3,4-dimethylbenzylidene) sorbitol, (iii) 1,3: 2,4-bis (p -Methylbenzylidene) sorbitol, (iv) 1,3: 2,4-di-O-benzylidenesorbitol, (v) an acid neutralizing agent that is at least one metal oxide, (vi) at least one metal carbonate An acid neutralizing agent which is a salt, selected from the group consisting of (vii) at least one natural or synthetic hydrotalcite and (viii) a mixture of any two or more of all of (i) to (vii). 27. The composition of claim 26. 36. The composition according to claim 35, wherein (a) used is at least one organic phosphite or at least one organic phosphonite or both. 36. The composition according to claim 35, wherein (a) used is tri (2,4-di-t-butylphenyl) phosphite. 27. The composition of claim 26, having a compression hardness of at least 10 pounds per inch. (I) at least one particulate organic phosphite, (ii) at least one organic phosphonite, (iii) at least one organic phosphonate, and (iv) in (i), (ii) and (iii) A compressed and solidified particulate polymer additive composition in the form of a dry granule exclusively made from at least one component selected from the group consisting of any two or all three mixtures, wherein the composition comprises The in-situ desolvation particle surface of the particles is at least partially solvated of the organic phosphite, organic phosphonite and / or organic phosphonate used in forming the composition, exclusively or substantially exclusively. A composition which is held together in a compacted, dry, granular form by interconnecting them together. 40. The composition of claim 39, wherein said at least one component used is at least one organic phosphite or at least one organic phosphonite or both. 40. The composition of claim 39, wherein said at least one component used is tri (2,4-di-t-butylphenyl) phosphite. A method for producing a compressed solidified granular polymer additive composition in the form of a dry granule,
1) (A) (i) granular organic phosphite, (ii) granular organic phosphonite, (iii) granular organic phosphonate, and any of (iv) (i), (ii) and (iii) One or more components selected from the group consisting of two or all three mixtures and (B) can evaporate at the lowest melting point or lower than the initial melting temperature of the one or more components of (A). Producing a paste from an inert organic processing solvent;
2) compressing and shaping the paste so that the solid used in forming the paste does not melt or substantially does not melt to form a wet compacted composition in granular form; 3) evaporating the processing solvent from the wet compacted solidified composition in granular form and drying it to produce a dry compacted granular polymer additive composition in granular form;
A method comprising: 43. The method of claim 42, wherein the one or more components of (A) used are at least one organic phosphite or at least one organic phosphonite or both. 43. The method of claim 42, wherein said one or more components of (A) used are tri (2,4-di-t-butylphenyl) phosphite. 43. A composition in the form of dry granules made by the method of claim 42, wherein the at least partially solvated particles of (A) are dried or desolvated exclusively or substantially exclusively. A composition having the resulting compression hardness and physical integrity. 44. A composition in the form of a dry granulate made by the method of claim 43, wherein the at least partially solvated particles of (A) are exclusively or substantially exclusively subjected to drying and desolvation. A composition having the resulting compression hardness and physical integrity. 45. A composition in the form of a dry granulate made by the method of claim 44, wherein the at least partially solvated particles of (A) are dried or desolvated exclusively or substantially exclusively. A composition having the resulting compression hardness and physical integrity.